Treatment of coals, tars, mineral oils, and the like



' Aug. 7, 19341 MHER 7 ',1,969,422

Nov. '29, 1930 2 Sheets-Sheet 1 1 E zuamzzwmr INVENTOR ATTORNEYS m W W W M W5 M. PIER Aug. 7, 1934.

TREATMENT OF GOALS, TABS, MINERAL OILS, AND THE LIKE Filed Nov. 29, 1930 2 Sheets-Sheet 2 INVENTOR.

A TTORNEYS.

Patented Aug. 7, 1934 TREATMENT OF GOALS, TA RS, MINERAL OILS, AND THE LIKE Mathias Pier, Heidelberg, Germany, signorto Standard-I. G. Company, Linden, N."J., a corporation of Delaware I Application November 29, 1930, Serial No. 498,939

In Germany December 3, 1929 4 Claims.

The present invention relates to improvements in and materials for the treatment of coals, tars, mineral oils and the like.

In the treatment of carbonaceous materials,

such as coals of all varieties, tars, mineral oils and the like, their distillation and conversion products and residues with hydrogen or gases supplying hydrogen at elevated temperatures, if desired under pressure, and in particular in destructive hydrogenation, the inner parts of the apparatus which come into contact with the hot reacting materials are frequently strongly corroded,

and the economy of the processis injuriously' affected by the inconvenience in working consequent thereon. This phenomenon, which takes place mainly in the reaction chamber, but which also takes place in the adjacent hot parts such as the supply and exit pipes, the preheaters, regenerators and the like, is caused by the presence of substances which injuriously affect the material under th working conditions. These injurious substances are mainly the hydrogen and sulphur .compounds arising .from the initial materials combined with the action of the carbonaceous materials and of the pressure usually present. In the treatment of coals, tars, mineral oils and the like with hydrogen at elevated temperatures constructional materials must therefore be employed which are capable of withstanding the injurious influences of hydrogen and suphur compounds in cases when the initial materials contain sulphur, as for example most kinds of coal, and crude oils, in particular crude American oil, Mexican Panuco oil, asphalts, pitches and the like.

I have now found that the corrosion on the constructional materials of the apparatus is entirely avoided by constructing the parts, which are liable to come into contact with the hot solid, liquid or gaseous reaction materials containing sulphur, wholly or partly of a metallic material (under which expression 1 understandmetals,

and alloys) which is stable or to a great extent stable to hydrogen and which is provided on the inside with a coating or lining which is insensitive to sulphur or itscompounds. Alloyed steels, which contain for example from 1 to 6 per cent of chromium alone or together with other elements such as aluminium, tungsten, vanadium, cobalt, manganese, nickel and the like and which are not sufliciently resistant to sulphur may be employed for the preparation of the outer walls of the reaction vessel which are stable to hydrogen and which if desired may be pressure bearing walls, or for the preparation of other parts of the apparatus, which are not exposed to the action of sulphur or compounds thereof. Thus for example alloyed steels having the following compositions may be employed with advantage for the preparation of the outer walls:

(1) iron containing 1 per cent of chromium,

0.2 per cent carbon; v I

(2) iron containing 3.8 per cent of nickel, 1.6 per centof chromium and 0.22 per cent of carbon; (3) iron containing-2.5 per cent of chromium, 11 per cent oftungsten and 0.3 per cent' of carbon; (4) iron containing 5.2 per cent of chromium, 2 per cent of nickel, 0.3 per cent of vanadium and 0.12 per cent of carbon;

(5) iron containing '1 per cent of chromium, 115.5 per cent of manganese and 0.2 per cent of car- (6') iron containing 4 per cent of chromium, 16 per cent of tungsten, 8 percent of cobalt, 1.5 per cent of vanadium and 0.7 per cent of carbon.

It is to be understood, however, that the steels of vanadium and 0.3 per cent of suitable .for the purpose-in question are not replied to the inner wall of the vessel by the diffusion occurring when two metals are brought into contact with each other 'at high temperatures. This inner wall need not be stable to hydrogen and'may' consist of a thin lining or coating permeable to hydrogen, if necessary only a fraction of a millimeter in thickness. ,It may be applied for example electrolytically.. Alloyed steels may also be provided with a coating ofaluminium which has been prepared by calorizing, whereby the alloyed steel is embedded in aluminium powder and heated, or painted with aluminium bronze or sprayed with aluminium and then heated. By the same process the parts'of the apparatus which come into contact with the hot reacting materials may also be provided with coatings of other metals having the same action. The walls of the vessel prepared from material which is stable to hydrogen may also be provided with coatings of pable of reacting with the reacting components.

In cases when the outer material stable to hydrogen is exposed to high pressures it is preferable to surround it with ordinary steel, provided if desired with de-aerating holes, to take up the pressure. The vessel and the inlet and outlet pipes and the like would then consist of an outer pressure bearing wall which surrounds a wall stable to hydrogen which is provided on the inner side with a coating or lining stable to sulphur.

The apparatus according to the present invention has the great advantages that the jacket stable to hydrogen need not be prepared from ma-,- terial stable to sulphur which is usually expensive, and that the inner protecting layer which is stable to sulphur may be very thin since the hydrogen which diffuses through in this case is retained by the outer jacket or cannot injure it.

The nature of the invention will be further described with reference to the accompanying drawings which illustrate arrangements of apparatus according to this invention, but the invention is not restricted to these arrangements.

Figures 1, 2 and 3 shows in longitudinal sec- Referring to Figure 1 numeral 1 denotes the wall of a reaction vessel which is covered with a coating 2 consisting of an iron alloy containing 6 per cent of chromium. The inner surface of this coating is provided with a further thin coating 3 consisting of silver, molybdenum, chromium or a zinc alloy.

Figure 2 shows a vessel the wall 1 of which is provided with holes 4, the walls being coated with a layer 2 consisting of an iron alloy'which contains 5.2 per cent of chromium, 2 per cent of nickel, 0.3 per cent of vanadium and 0.12 per cent of carbon. The inner surface of the layer 2 is provided with a thin lining 3 of zinc or aluminium. The outer surface of the said layer is provided with a groove 5 winding spirally round it.

Figure 3 shows a reaction vessel the wall 1 of which is provided with a coating 2 consisting of an iron alloy containing 3.8 percent of nickel,

1.6 per cent of chromium 'and 0.22 per cent of carbon. Between the coating 2 and the wall 1 is a free space 6 which is filledwith an insulating material such as asbestos or the like, or with nitrogen or the like. When filling the said free space with a gas it is necessary that the pressure of the. latter should be as great as the pressure in the reaction space. The inner surface of the coating 2 is lined with a thin layer of brass 3.

The following examples will further illustrate the nature of this invention, but the invention is not restricted to these examples.

Example 1 atmospheres at the inlet '7 shown in Figure 4' through a preheater 8 which consists of an iron alloy containing 13 per cent of chromium and 0.15 per cent of carbon and which is heated with hot gases. The materials preheated to a temperature of about 440 C. are then passedinto the reaction vessel 9 where, while liquid at about 450 0., they are brought intocontact'with a catalyst consisting of molybdic 'acid and zinc oxide. The reaction vessel is lined with a coating 2 consisting of an iron alloy containing 3.3 per cent of chromium, 1.5 per cent of nickel, 0.5 per cent of manganese and 0.1 per centof carbon. The inner surface of this coating is provided with a layer 3 consisting of aluminium, the thickness of which is exaggerated in the drawings for the sake of clearness. The gases and vapors leaving the reaction vessel at the outlet 10 are passed through condenser 11 which consists of an iron alloy containing 3 per cent of nickel, 1.5 per cent of chromium and 0.3 per cent carbon. The inner surface of the condenser and of the preheater is also provided with a layer 3 consisting of aluminium. This layer is prepared by applying aluminium bronzeto the single parts of the apparatus and then exposing them in an atmosphere of hydrogen to a temperature of about from 900 to 1000 C. In this manner a firm coating is obtained which is not substantially attacked by sulphur even after a long duration of the reaction. 15 per cent of constituents boiling to 180 C. and 60 per cent of middle oils are obtained from the initial materials.

0 Example 2 A Mexican Panuco oil containing 4.5 per cent of sulphur is brought together with hydrogen into contact with a catalyst prepared from tungstic acid, arsenic acid and manganese carbonate at 450 C. under a pressure of 200 atmospheres ina high pressure vessel. The whole of the high pressure apparatus is constructed of a material which consists of 5.3 per cent of chromium, 1.8 per cent of nickel, 0.1 per cent of carbon and the remainder iron. The parts of the apparatus which come into contact with the hot reacting materials are provided with a thin coating consisting of 60 per cent of copper and '40 per cent of zinc, which is prepared by immersing the parts of the apparatus in a liquid melt of the metals. The coating is not attacked by sulphur even after use for long periods of time. In this manner 20 per cent of constituents boiling at temperatures up to 180 C. and 60 per cent of middle oil are obtained from the initial materials.

What I claim is:-

1. An apparatus suitable for heat-treating carbonaceous materials with hydrogen, of which the parts liable to come into contact with the hot materials are composed of a base consisting of an alloyed steel containing from 1 to 6 per cent of chromium, which is internally lined with a coating of a metallic material selected from the group consisting of zinc and zinc alloys.

2. The process of destructively hydrogenating hydrocarbon products containing sulphur with hydrogen under a temperature and pressure suit-. able for destructive hydrogenation which comprises effecting the destructive hydrogenation in a reaction space defined by a material resistant to sulphur under the conditions of the reaction and permeable to hydrogen selected from the class consisting of zinc and alloys of zinc and pre ventingescape of the hydrogen from the reaction space by backing said sulphur resistant material with a hydrogen resistant hydrogen impermeable shell composed of a chromium steel.

3. The process as defined in claim ZWherein said shell is composed of a chromium steel containing from 1 to 6 per cent of chromium.

4. The process as defined in claim 2 .wherein the hydrocarbon products comprise a hydrocarbon oil containing sulphur. andwherein the destructive hydrogenation is carried out at a temperature 145 of about 450 C. and a pressure of about 200 atmospheres.

MA'I'HIAS PIER. 

